CN103467890A - Strippable protective film and composition formula thereof - Google Patents
Strippable protective film and composition formula thereof Download PDFInfo
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- CN103467890A CN103467890A CN201310429915XA CN201310429915A CN103467890A CN 103467890 A CN103467890 A CN 103467890A CN 201310429915X A CN201310429915X A CN 201310429915XA CN 201310429915 A CN201310429915 A CN 201310429915A CN 103467890 A CN103467890 A CN 103467890A
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Abstract
The invention provides a strippable protective film which is excellent in adhesive performance and does not have peeling problem, and is applicable to temporary protection of articles. In particular, the stripping strength of the protective film is between 35g/cm and 100g/cm, so that the protective film can be easily stripped when being stripped from an article, and residual adhesive cannot be left on an adhered article. The protective film is prepared from a composition in a specific formula, the TI value of the composition is between 2.00 and 2.20, and the composition comprises a vinyl chloride-vinyl acetate copolymer, high and low molecular weight polyvinyl chloride emulsified polymer powder, a trimellitate plasticizer, a diisobutyrate mixed plasticizer, a phenol-free calcium-zinc stabilizing agent, smoked silica, aluminum hydroxide, barium sulfate and calcium carbonate.
Description
Technical field
The present invention relates to a kind of peelable protective film and composite formula thereof, can peel off easily and not stay peelable protective film and the composite formula thereof of cull after espespecially a kind of intermediate process.
Background technology
In the prior art; peelable protective film is a kind of film product that has bonding and dustproof scratch resistant function concurrently; through being usually used in temporarily protecting the outward appearance of article; or in the middle work flow of electronic package or optical module or between the shelf lives; for temporarily bonding and protect electronic package or optical module (hereinafter to be referred as by the glue thing) processed or that be stored; until in the middle of work flow complete or while formally using; can easily protective membrane be separated from being torn off by the glue thing, and can not injure by the glue thing.
Yet; peelable protective film of the prior art; a kind of acrylic copolymer protectiveness film that for example the open case of U.S. Pat 6211282 discloses; when bonding or fit to by the glue thing on the time; have the problem of peeling off under high-pressure washing; and; from being torn off by the glue thing the process of protective membrane; the bonding composition of protective membrane often can form the glue-line (hereinafter to be referred as cull) that is difficult for removing and be adhered to by the surface of glue thing; having causes wasting time and energy removes the defect of cull, therefore peelable protective film of the prior art still is improved space.
In addition; peelable protective film of the prior art; in manufacturing processed, need to use solvent and needs through crosslinked sclerosis; so that the environmental issue that solvent slop is arranged; especially peelable protective film is after process tears off use; but can not recycling, need be with waste disposal, do not have an environment protection meaning in fact.
Summary of the invention
For overcoming above-mentioned shortcoming; the invention provides a kind of peelable protective film; do not use solvent and crosslinked process of setting; by the suitably combination of resin and the collocation of different softening agent, have outside dimensional stabilizing, stable viscosity, bonding force appropriateness, water-repellancy and excellent heat stability, during use; also have the characteristics that can peel off easily, not break and not stay cull concurrently; especially do not use solvent, can reclaim circulation and re-use, the tool environment protection.
For the manufacture of the composition of peelable protective film of the present invention, use following special formulation composition, based on composition total weight, comprise
A) vinyl chloride-vinyl acetate copolymer, the K value, between 69～71, accounts for 10～65wt%; Wherein, the content of vinyl acetate between to for plastic is 1.0～12.5%, is preferably 4.0～6.9%;
B) high molecular weight pvc emulsion polymerization powder, the K value, between 77.5～81, accounts for 3～20wt%;
C) lower molecular weight PVC emulsifying polymer powder, the K value, between 73.0～76.5, accounts for 3～20wt%;
D) the benzenetricarboxylic acid ester plasticizer, account for 5～40wt%;
E two kinds of mixing of) Fu acid mixed radix ester plasticizer and diisobutyrate class softening agent are used, and account for 1～20wt%;
F) without the phenol calcium zinc stabilizer, account for 0.5～3wt%;
G) smoked silica (Fumed silica or title aerosil), account for 1～10wt%;
H) aluminium hydroxide, account for 0.1～10wt%;
I) barium sulfate, account for 0.1～20wt%;
J) calcium carbonate, account for 0.1～20wt%.
Peelable protective film of the present invention, outside the bonding and dustproof scratch resistant function of tool, also meet following conditional request, is applicable to making the peelable protective film for optical module:
1, the stripping strength of peelable protective film, between 35～100g/cm, during use, can be peeled off easily in tearing off process, and the glue-line of peelable protective film can be to not stayed cull by the glue thing;
2, the ovenable roasting property of peelable protective film tool, through 180 ℃ of bakings 10 minutes, and repeat same steps as and toast 3 times continuously, and the glue-line of peelable protective film still has toughness, and surface drying is good, inviscid problem;
3, the good sticking power of peelable protective film tool, be adhered to by the glue thing time, through following wherein one or more test conditions, still possesses the adhesive ability of not peeling off:
A) carry out frequency 46khz ultrasonic vibrating 5 minutes under temperature 45 C;
B) with 10kg/cm
2hydraulic pressure carries out high-pressure washing;
C) invade 60 ℃ of hot-water soaks 26 minutes;
D) the 3.17%NaOH basic solution that immerses 40 ℃ of temperature soaks 2 minutes; Or
E) the chloroazotic acid series acidic solution that immerses 46 ℃ of temperature soaks 2 minutes.
Embodiment
Peelable protective film of the present invention is to use the composition (hereinafter referred to as peelable composition) of tool special formulation of the present invention to be processed into through coating at normal temperatures; Except thering is viscosity stability, water-repellancy and thermostability, when bonding or fit to by the glue thing on, also have the characteristic of stripping strength between 35～100g/cm concurrently, and the characteristics that can peel off easily and not stay cull, especially do not use solvent, can reclaim circulation and re-use.
The peelable composition used, under 25 ℃ of room temperatures, the viscosity that the VT-04 viscometer records is between 400～600ps, use the DVII+Pro type rotational viscosimeter test (be designated hereinafter simply as and use the rotational viscosimeter test) of U.S. BROOKFIELD company, possesses shake-change property index (the Thixotropy Index imposed a condition as under " 0.5rpm viscosity/2.5rpm viscosity ", abbreviation TI value) physical property between 2.00～2.20, based on composition total weight, comprises following ingredients:
A) vinyl chloride-vinyl acetate copolymer, the K value, between 69～71, accounts for 10～65wt%; Wherein, the content of vinyl acetate between to for plastic is 1.0～12.5%, is preferably 4.0～6.9%;
B) high molecular weight pvc emulsion polymerization powder, account for 3～20wt%; Its mean polymerisation degree (Average Degree of polymerization, DP) between 1650～1850, K value (Fikentscher ' s Constant) between 77.5～81;
C) lower molecular weight PVC emulsifying polymer powder, account for 3～20wt%; Its mean polymerisation degree between 1350～1550, K value between 73.0～76.5;
D) the benzenetricarboxylic acid ester plasticizer, account for 5～40wt%;
E) diisobutyrate class softening agent, account for 1～20wt%; And described diisobutyrate class softening agent is 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate (2,2,4-trimethyl-1,3-pentanediol diisobutyrate, TXIB) softening agent, wherein, benzenetricarboxylic acid ester plasticizer and 2,2,4-trimethylammonium-1, the usage quantity ratio of 3-pentanediol diisobutyrate softening agent is 1.0～9.0, but with 4.0～6.0 the bests;
F) without the phenol calcium zinc stabilizer, account for 0.5～3wt%;
G) smoked silica, account for 1～10wt%;
H) aluminium hydroxide, account for 0.1～10wt%;
I) barium sulfate, account for 0.1～20wt%;
J) calcium carbonate, account for 0.1～20wt%.
The present composition is many, contain solid, liquid raw material, feeding sequence can affect viscosity to be changed, for control group compound stable viscosity, and do not use under the solvent adjustment, first with softening agent dissolved chlorine ethene-vinyl acetate copolymerization powder, lower molecular weight PVC emulsifying polymer powder, then dissolve high molecular weight pvc emulsion polymerization powder, attention can not first drop into high molecular emulsion polymerization powder, in case viscosity hurriedly rises, stir after 40 minutes standing more than 2 hours, make the copolymerization powder, the abundant swelling of emulsion polymerization powder, guarantee stable viscosity, smoked silica and aluminium hydroxide all can significantly improve viscosity, under low rate mixing, finally drop into, its manufacture method feeding sequence is as following:
(1) first the benzenetricarboxylic acid ester plasticizer is dropped into to mixing machine, then drop into the diisobutyrate softening agent, then drop into one package stabilizer; Start paddle, low rate mixing also sequentially slowly drops into vinyl chloride-vinyl acetate copolymer, then drops into lower molecular weight PVC emulsifying polymer powder, finally drops into high molecular weight pvc emulsion polymerization powder, stirs after 40 minutes standing more than 2 hours;
(2) start paddle and improve stirring velocity, sequentially dropping into barium sulfate, calcium carbonate;
(3) stir reduction of speed after 5 minutes and stir, finally drop into smoked silica and aluminium hydroxide;
(4) stirring after 30 ± 5 minutes and measure viscosity, is 400～600ps 25 ℃ of lower viscosity, churning time apparent viscosity and extend or shorten.
Described vinyl chloride-vinyl acetate copolymer (Vinyl Chloride-Vinyl Acetate copolymers) is jointly to be polymerized by vinylchlorid and two kinds of monomers of vinyl acetate between to for plastic, and the content of vinyl acetate between to for plastic is higher, the bonding strength of vinyl chloride-vinyl acetate copolymer is thereupon high, consideration film forming tack is good easily to be peeled off again, the content of vinyl acetate between to for plastic should be suitable, can not be higher or too low.Therefore, described vinyl chloride-vinyl acetate copolymer has the high tenacity of vinylchlorid and strong viscosity and the plasticity-of erosion resistance and vinyl acetate between to for plastic, the film dimensions good stability is processed in coating, but high-temperature baking resistant and hot-water soak, and prepared film, possess acidproof not only alkaline-resisting, protection against the tide but also waterproof, nonflammable and not combustion-supporting characteristic.
But described high molecular weight pvc emulsion polymerization powder possesses the characteristic of low viscosity and low-temperature heat gel, can be coated with and be processed into film at normal temperatures.And prepared film, possess the characteristic of water tolerance and anti-electrostatic.
Described lower molecular weight PVC emulsifying polymer powder possesses proper viscosity, has good demoulding while making film.
In peelable protective film composition of the present invention, comprise the use of arranging in pairs or groups together of vinyl chloride-vinyl acetate copolymer and the PVC emulsifying polymer powder of different mean polymerisation degree, under the condition of not using solvent, choose appropriate vinyl chloride-vinyl acetate copolymer, be used in conjunction with again appropriate height, low-molecular-weight PVC emulsifying polymer powder, can make and possess the most suitable bonding strength, the peelable protective film of tension intensity and toughness, when as the protective membrane use, have concurrently and can peel off easily, do not break and do not stay the characteristics of cull, simultaneously, it is the most stable that the three mixes the shake-change property index (TI value) that forms glue, little favourable coating processing makes a variation.
Described benzenetricarboxylic acid ester plasticizer can be selected from benzenetricarboxylic acid trimethyl (Trimethyl trimellitate, TMTM), the own ester of benzenetricarboxylic acid (Triethyl trimellitate, TETM), the own ester of benzenetricarboxylic acid three (Trihexyl trimellitate, THTM), different three monooctyl esters (the Trisooctyl trimellitate of benzenetricarboxylic acid, TIOTM) or benzenetricarboxylic acid three monooctyl esters (Tri (2-ethylhexyl) trimellitate, TOTM) wherein a kind of independent use or more than one mixing use, tool low migration under 100～180 ℃ of bakings of high temperature, can possess surface drying, and it is inviscid, and still possess excellent in toughness.
Described 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate (TXIB), be a kind of not containing the non-toxic, environmental friendly softening agent of phenyl ring, with vinyl chloride-vinyl acetate copolymer, easily mixes, except the viscosity that can reduce peelable composition of the present invention, and can promote the flow characteristics of peelable composition of the present invention, make the stable viscosity of peelable composition of the present invention and be difficult for sneaking into bubble, be suitable for coating processing most and make film; And, prepared finished film smooth in appearance, its surperficial tool anti-soil and antiwear property (or claiming scratch resistance), during use, be not prone to scratch.
In peelable composition of the present invention, comprise the use of arranging in pairs or groups of benzenetricarboxylic acid ester plasticizer together with the diisobutyrate softening agent, and do not use solvent, by the allotment of both different usage quantitys, wherein, benzenetricarboxylic acid ester plasticizer and 2,2,4-trimethylammonium-1, the usage quantity ratio of 3-pentanediol diisobutyrate softening agent is 1.0～9.0, but with 4.0～6.0 the bests, can reach to described peelable composition is suitably adjusted its viscosity and guaranteed and possess viscosity stability, not only contribute to described peelable composition is processed into to film, and make prepared film possess excellent flexibility, toughness and scratch resistant property, especially through 180 ℃ of bakings in 10 minutes 3 times, still possess toughness, its drying property is also good, when the protective membrane first surface 100～120 ℃ of prebake conditions after 3 minutes, while printing second, first surface and printing table are inviscid, be more suitable for the purposes as peelable protective film, and in tearing off the process of peelable protective film, can guarantee that peelable protective film can not break.
Described is not containing nonyl phenol (Nonyl Phenol), containing dihydroxyphenyl propane (Bis-Phenol-A), not containing the stablizer of three kinds of solvents of phenol (Phenol) without the phenol calcium zinc stabilizer, its objective is processing procedure containing the phenol solvent and improves the resistance toheat of peelable composition of the present invention.
The purposes of described smoked silica, be to use as adjusting adhesive, and for adjusting the viscosity of peelable composition of the present invention, the stream that prevents from hanging down also can prevent the stopping composition precipitation.The structure of described smoked silica, be preferably particle diameter between 5～50nm, and surface-area is between 50～600m
2/ g.
For preventing viscosity drastic change in time, coordinate smoked silica to use aluminium hydroxide to adjust the sticky thickening effectiveness that has, aluminium hydroxide has the both sexes characteristic simultaneously, can with acid-respons again can with alkali reaction, the function of performance acid-and base-resisting, be also characteristics of the present invention.2～6 times that smoked silica consumption is aluminium hydroxide is good, and the variate TI (Thixotripic Index) that shakes of this two things consumption capable of regulating control group compound is good 2.00～2.20.
In addition, the diisobutyrate class softening agent in peelable composition of the present invention, be a kind of nonionogenic tenside, both had lipophilic group, has again hydrophilic radical.And described aluminium hydroxide has both sexes, can with acid-respons again can with alkali reaction.Therefore, in peelable composition of the present invention, described aluminium hydroxide is arranged in pairs or groups together with described diisobutyrate softening agent use, can promote described nonionogenic tenside to form micelle, and strengthen thus the surface tension of tensio-active agent, make peelable composition of the present invention reach the effect of tackify.
The purposes of described barium sulfate, for improving the performance of peelable composition of the present invention, comprise and improve electric insulating quality, resistance to heat distorsion, anti-opticity and thermostability, reduce linear expansivity and shrinking percentage, increase thermal conductivity, improve glue-line stability, increase thermotolerance and physical strength, the viscosity etc. that changes the mobility of gluey peelable composition or regulate peelable composition.The structure of barium sulfate of the present invention, be preferably median size between 1～50nm, for wear resistance, the acid resistance that improves peelable protective film.
The structure of described calcium carbonate; be preferably median size between 30～100nm; for improving the toughness of peelable composition of the present invention, and reduce the shrinking percentage of prepared peelable protective film, the surface flatness of promoting described peelable protective film and scratch resistance characteristic.When peelable composition especially of the present invention is used the nanometer calcene as weighting agent, peelable composition of the present invention possesses better thermostability and dispersiveness, is more suitable for making the peelable protective film for optical module.
Do not using under solvent, peelable composition of the present invention, possess the physical property of TI value (under 0.5rpm viscosity/2.5rpm viscosities) between 2.00～2.20, and shake-change property is little, stable viscosity, the most applicable coating processing.And, in the process of coating processing, peelable composition of the present invention, the anti-fluidity that hangs down of tool, not there will be vertical flow phenomenon.
And the peelable protective film that peelable composition according to the present invention makes with coating processing can meet following conditional request:
1. the stripping strength of peelable protective film, between 35～100g/cm, is preferably between 45～80g/cm, in tearing off process, can peel off easily, and the glue-line of peelable protective film can be to not being stayed cull by the glue thing;
2. the ovenable roasting property of peelable protective film tool, through 180 ℃ of bakings 10 minutes, and repeat same steps as and toast 3 times continuously, and the glue-line of peelable protective film still has toughness;
3. the good sticking power of peelable protective film tool, be adhered to by the glue thing time, after following test condition, still do not have the problem of peeling off:
Carry out frequency 46khz ultrasonic vibrating under the temperature 45 C condition 5 minutes, at pressure 10kg/cm
2(3.17%NaOH) basic solution that carries out high-pressure washing under condition, invades 60 ℃ of hot-water soaks 26 minutes, immerses 40 ℃ of temperature soaks 2 minutes, (chloroazotic acid series) acidic solution of immersing 46 ℃ of temperature and soaks 2 minutes.
Below enumerating embodiment and comparative example illustrates peelable composition of the present invention and is applicable to make a kind of peelable protective film.Peelable composition and prepared peelable protective film that embodiment and comparative example are used, test its physical property and characteristic according to following appraisal procedure.
1. Nian Du ︰
Under 25 ℃ of conditions of temperature, the viscosity of using the VT-04F type viscometer of Japanese RION company to test peelable composition.
2. the shake-change property index (or claims TI value) ︰
Under 25 ℃ of conditions of temperature, the TI value that the DVII+Pro type rotational viscosimeter of use U.S. BROOKFIELD company is tested peelable composition.
Ce amount Fang Fa ︰, under the 2.5rpm rotating speed, after making the stable viscosity of peelable composition, waits for approximately 3 minutes, and surveying its viscosity is V1; Under the 0.5rpm rotating speed, after making the stable viscosity of peelable composition, wait for equally approximately 3 minutes, surveying its viscosity is V
2.Wherein, TI value=10V
2/ V
1.
3. Dinging Xing of viscosity Wen ︰
Under 25 ℃ of conditions of temperature, peelable composition is statically placed in dust free chamber after 24hr to the viscosity of using the DVII+Pro type rotational viscosimeter of U.S. BROOKFIELD company to test peelable composition.
4. resist the fluidity that hangs down:
Gluey peelable composition is after coating, without the flow phenomenon that hangs down.
5. Gan Zao ︰
Under 100～120 ℃ of conditions of temperature; by the first surface of peelable protective film surface prebake conditions after 3 minutes; peelable protective film is placed on printing table its second surface printed, and the first surface of peelable protective film surface needs to meet with printing table inviscid.
6. Nai toasts Xing ︰
Under 180 ℃ of conditions of temperature, after peelable protective film is toasted to 10 minutes, then repeat to toast 3 times, the glue-line of peelable protective film still has toughness.
7. divesting Xing ︰
By after peelable protective film and 3M adhesive tape (tape) laminating, the 3M adhesive tape is divested, the 3M adhesive tape need not have cull to occur.
8. adhering to Xing ︰
Composition is coated by the glue thing, and after 150 ℃ * 2 minutes film forming, peelable protective film is attached to by the glue thing, then with the adhesive ability of following 5 kinds of methods test peelable protective film.After test, then the visual observations peelable protective film whether can with by the glue thing, peeled off, problem does not appear peeling off, represent that peelable protective film has splendid adhesive ability:
A. ultrasonic vibrating:
Under the temperature 45 C condition, with frequency 46kHz ultrasound to adhere to peelable protective film by glue thing concussion 5 minutes.
B. water jets under high pressure is impacted:
With pressure 10kg/cm
2water column to being attached to by the peelable protective film of glue thing, rinsed.
C. hot-water soak:
Under 60 ℃ of conditions of water temperature, will adhere to being soaked 26 minutes by the glue thing of peelable protective film.
D. alkali resistance:
In sodium hydroxid (NaOH) solvent of 40 ℃ of temperature and concentration 3.17%, will adhere to being soaked 2 minutes by the glue thing of peelable protective film.
E. acid resistance:
In the chloroazotic acid series solvent of 46 ℃ of temperature, will adhere to being soaked 2 minutes by the glue thing of peelable protective film.
9. stripping strength:
Get the peelable protective film of 1 centimeter of width, from it, fit by the glue thing, peeled off the time, measure its 180 the degree direction stripping strength.
The stripping strength of peelable protective film is under the condition of 35～100g/cm, and peelable protective film not there will be cull in tearing off process.
[embodiment 1-6]:
Formula (numeral is weight part) according to table 1, be modulated into respectively the peelable composition of embodiment 1-6, then measure respectively its physical property, comprises viscosity, TI value, viscosity stability and the anti-fluidity that hangs down, and measuring result is as shown in table 2.
Modulated peelable composition is made respectively to peelable protective film with coating processing, then measure respectively its characteristic, comprise ovenable roasting property, divesting property, tack and stripping strength, measuring result is as shown in table 3.
[comparative example 1-4]:
Formula (numeral is weight part) according to table 1, be modulated into respectively the peelable composition of comparative example 1-4, then measure respectively its physical property, comprises viscosity, TI value, viscosity stability and the anti-fluidity that hangs down, and measuring result is as shown in table 2.
Modulated peelable composition is made respectively to peelable protective film with coating processing, then measure respectively its characteristic, comprise ovenable roasting property, divesting property, tack and stripping strength, measuring result is as shown in table 3.
Table 1 embodiment and comparative example formula
Annotate 1: vinyl chloride-vinyl acetate copolymer comprises 5.0 ﹪ vinyl acetate between to for plastics (Vinyl Acetate), and its K value is 70;
Annotate 2: vinyl chloride-vinyl acetate copolymer comprises 13.0 ﹪ vinyl acetate between to for plastics (Vinyl Acetate), and its K value is 50
Annotate 3: the model PR1069PVC emulsifying powder product that Taiwan plastics industry limited-liability company manufactures, its K value is 77.5～81;
Annotate 4: the model PR415PVC emulsifying powder product product that Taiwan plastics industry limited-liability company manufactures, its K value is 73.0～76.5;
Annotate 5:2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate.
The peelable composition physical property of table 2 embodiment and comparative example
Annotate 5: viscosity stability with excellent, good, can, bad to the amount of commenting grade.
The peelable protective film characteristic of table 3 embodiment and comparative example
Annotate 6: under 100～120 ℃, the glue-line first surface surface condition of peelable protective film, prebake conditions is after 3 minutes, observes the first surface surface and has with printing table, inviscid.
Annotate 7: the glue-line of peelable protective film still has toughness after baking, with excellent, good, can, bad to the amount of commenting grade.
Annotate 8: immerse in sodium hydroxid (NaOH) solvent of 40 ℃ of temperature and concentration 3.17% 2 minutes, with excellent, good, can, badly for the amount of commenting alkali resistance, adhere to and not peel off grade.
Annotate 9: immerse in 46 ℃ of chloroazotic acid series solvents of temperature 2 minutes, with excellent, good, can, badly for the amount of commenting acid resistance, adhere to and not peel off grade.
result:
1, the peelable composite formula of comparative example 1-4, only select wherein one to two kind of softening agent collocation with single kind of vinyl chloride-vinyl acetate copolymer or high and low molecular weight polyisoprene vinylchlorid emulsion polymerization powder to use, and do not make smoked silica and the aluminium hydroxide of apparatus adjusting adhesive purposes.
And the peelable composition of embodiment 1-6, select the use of arranging in pairs or groups together with the PVC emulsifying polymer powder of vinyl chloride-vinyl acetate copolymer and high and low molecular weight, and collocation selects the benzenetricarboxylic acid ester plasticizer to use together with the diisobutyrate softening agent, allocate again other special component formula, compositions such as the smoked silica that interpolation tool adjusting adhesive purposes is arranged and aluminium hydroxide.
In comparison, aspect viscosity, TI value, viscosity stability and the anti-fluidity that hangs down of the peelable composition of performance, according to shown in table 2, the physical property of the peelable composition of embodiment 1-6, all many than the peelable composition excellence of comparative example 1-4.
Especially the TI value of the peelable composition of embodiment 1-6, between 2.05～2.16, shake-change property is little, and stable viscosity is conducive to coating processing, and prepared peelable protective film also is conducive to place and store.
2, the peelable protective film that embodiment 1-6 makes, according to shown in table 3, possess stripping strength between 50～80g/cm characteristic, tearing off the condition that not there will be cull in process while meeting stripping strength when peelable protective film between 35～100g/cm.
The peelable protective film that comparative example 1-4 makes, according to shown in table 3, within its stripping strength does not drop on the scope of 35～100g/cm.Comparative example 3 full dose vinyl chloride-vinyl acetate copolymers, the protective membrane stripping strength of comparative example 4 high-content vinyl acetate between to for plastics is higher, is difficult for peeling off.
In comparison, the peelable protective film of embodiment 1-6, possess and can peel off easily and can be to do not stayed the excellent characteristics of cull by the glue thing.
3, with the preceding paragraph explanation; ovenable roasting property, divesting property and tack ability in the performance peelable protective film; especially shatter-proofly swing, anti-flushing, water tolerance, acid resistance, alkali resistance aspect; according to shown in table 3; the physical property of the peelable protective film that embodiment 1-6 makes, all than the peelable protective film excellence of comparative example 1-4.
Accordingly, the peelable protective film of embodiment 1-6 has splendid adhesive ability, when conduct temporarily protects purposes to use on being attached to by the glue thing, not there will be the problem of peeling off.
4, the acid resistance of embodiment 4-6, alkali resistance are adhered to and are not peeled off, and are better than embodiment 1-3 and more are better than comparative example 1-4, and the impact effect of signify hydrogen aluminum oxide and barium sulfate is good.
Claims (9)
1. the composition of a peelable protective film; it is characterized in that: do not using under solvent; use the vinyl chloride-vinyl acetate copolymer of specific vinyl acetate content to coordinate speciality plasticizer jointly to form with high and low molecular weight polyisoprene vinylchlorid emulsion polymerization powder; with rotational viscosimeter, test; possess and impose a condition as the TI value under 0.5rpm viscosity/2.5rpm viscosity between 2.00～2.20 physical property; based on composition total weight, comprise following Cheng Fen ︰
A) vinyl chloride-vinyl acetate copolymer, the K value, between 69～71, accounts for 10～65wt%; Wherein, the content of vinyl acetate between to for plastic is 1.0～12.5%;
B) high molecular weight pvc emulsion polymerization powder, its mean polymerisation degree between 77.5～81, accounts for 3～20wt% between 1650～1850, K value;
C) lower molecular weight PVC emulsifying polymer powder, its mean polymerisation degree between 1350～1550, K value between 73.0～76.5; Account for 3～20wt%;
D) the benzenetricarboxylic acid ester plasticizer, account for 5～40wt%;
E) 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate (TXIB) softening agent, account for 1～20wt%; Wherein, benzenetricarboxylic acid ester plasticizer and 2,2,4-trimethylammonium-1, the usage quantity ratio of 3-pentanediol diisobutyrate softening agent, be 1.0～9.0;
F) without the phenol calcium zinc stabilizer, account for 0.5～3wt%;
G) smoked silica, account for 1～10wt%;
H) aluminium hydroxide, account for 0.1～20wt%;
I) barium sulfate, account for 0.1～20wt%, and wherein, the median size of described barium sulfate, between 1～50nm;
J) calcium carbonate, account for 0.1～20wt%, and wherein, the median size of described calcium carbonate, between 30～100nm.
2. composition as claimed in claim 1, wherein, the vinyl acetate content of described vinyl chloride-vinyl acetate copolymer is 4.0～6.9%.
3. composition as claimed in claim 1, wherein, described benzenetricarboxylic acid ester plasticizer is selected from wherein a kind of independent use or more than one mixing the use of benzenetricarboxylic acid trimethyl (TMTM), the own ester of benzenetricarboxylic acid (TETM), the own ester of benzenetricarboxylic acid three (THTM), different three monooctyl esters of benzenetricarboxylic acid (TIOTM) or benzenetricarboxylic acid three monooctyl esters (TOTM).
4. composition as claimed in claim 1, wherein, described benzenetricarboxylic acid ester plasticizer and 2,2,4-trimethylammonium-1, the usage quantity ratio of 3-pentanediol diisobutyrate softening agent, be 4.0～6.0.
5. composition as claimed in claim 1, be according to following feeding sequence get ︰ processed
(1) first the benzenetricarboxylic acid ester plasticizer is dropped into to mixing machine, then drop into the diisobutyrate softening agent, then drop into one package stabilizer; Start paddle, low rate mixing also sequentially slowly drops into vinyl chloride-vinyl acetate copolymer, then drops into lower molecular weight PVC emulsifying polymer powder, finally drops into high molecular weight pvc emulsion polymerization powder, stirs after 40 minutes standing more than 2 hours;
(2) start paddle and improve stirring velocity, sequentially dropping into barium sulfate, calcium carbonate;
(3) stir reduction of speed after 5 minutes and stir, sequentially drop into smoked silica, aluminium hydroxide;
(4) stirring after 30 ± 5 minutes and measure viscosity, is 400～600ps 25 ℃ of lower viscosity, churning time apparent viscosity and extend or shorten.
6. as 1 described composition of claim the, wherein, the particle diameter of described smoked silica is between 5～50nm, and surface-area is between 50～600m
2/ g.
7. the peelable protective film that the composition of a right to use requirement 1 is made, is characterized in that possessing the characteristic of stripping strength between 35～100g/cm.
8. peelable protective film as claimed in claim 7, possess the characteristic of stripping strength between 45～80g/cm.
9. peelable protective film as claimed in claim 7 or 8, through following wherein one or more test conditions, still possesses the adhesive ability of not peeling off:
A) carry out frequency 46khz ultrasonic vibrating 5 minutes under temperature 45 C;
B) with 10kg/cm
2hydraulic pressure carries out high-pressure washing;
C) invade 60 ℃ of hot-water soaks 26 minutes;
D) the 3.17%NaOH basic solution that immerses 40 ℃ of temperature soaks 2 minutes; Or
E) the chloroazotic acid series acidic solution that immerses 46 ℃ of temperature soaks 2 minutes.
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| CN201310429915.XA CN103467890B (en) | 2013-09-18 | 2013-09-18 | A kind of peelable protective film and composite formula thereof |
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| CN103467890A true CN103467890A (en) | 2013-12-25 |
| CN103467890B CN103467890B (en) | 2016-04-20 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756455A (en) * | 2014-01-14 | 2014-04-30 | 北京海斯迪克新材料有限公司 | High-temperature resistant strippable protection coating and preparation method thereof |
| CN104761960A (en) * | 2015-03-21 | 2015-07-08 | 广东南海启明光大科技有限公司 | 3D curved surface shielding liquid capable of spraying and thermocuring and preparation method thereof |
| CN105838276A (en) * | 2016-01-29 | 2016-08-10 | 宁波吉象塑胶制品有限公司 | Adhesive tape preparation method |
| CN108034163A (en) * | 2017-12-05 | 2018-05-15 | 沈阳化工股份有限公司 | A kind of PVC vehicle glasses anti-fog film and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097788A (en) * | 1994-06-04 | 1995-01-25 | 潘治平 | Transfer type easy erasing pressure sensing glue |
| CN1193033A (en) * | 1998-03-05 | 1998-09-16 | 晏林宝 | Hot-dipping stripped plastic protective film for plastics, mfg. method and application thereof |
| US20010005733A1 (en) * | 1996-04-23 | 2001-06-28 | Rinrei Wax Co., Ltd. | Aqueous dispersion of a peelable coating composition |
| CN101892019A (en) * | 2009-05-20 | 2010-11-24 | E.I.内穆尔杜邦公司 | Strippable multilayer-structure surface protective film and product thereof |
| CN102219965A (en) * | 2011-05-20 | 2011-10-19 | 潍坊胜达科技股份有限公司 | Antistatic flame-resistant environmentally stable peelable protective film and preparation method thereof |
-
2013
- 2013-09-18 CN CN201310429915.XA patent/CN103467890B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097788A (en) * | 1994-06-04 | 1995-01-25 | 潘治平 | Transfer type easy erasing pressure sensing glue |
| US20010005733A1 (en) * | 1996-04-23 | 2001-06-28 | Rinrei Wax Co., Ltd. | Aqueous dispersion of a peelable coating composition |
| CN1193033A (en) * | 1998-03-05 | 1998-09-16 | 晏林宝 | Hot-dipping stripped plastic protective film for plastics, mfg. method and application thereof |
| CN101892019A (en) * | 2009-05-20 | 2010-11-24 | E.I.内穆尔杜邦公司 | Strippable multilayer-structure surface protective film and product thereof |
| CN102219965A (en) * | 2011-05-20 | 2011-10-19 | 潍坊胜达科技股份有限公司 | Antistatic flame-resistant environmentally stable peelable protective film and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756455A (en) * | 2014-01-14 | 2014-04-30 | 北京海斯迪克新材料有限公司 | High-temperature resistant strippable protection coating and preparation method thereof |
| CN103756455B (en) * | 2014-01-14 | 2016-05-18 | 北京天山新材料技术有限公司 | A kind of high temperature resistant peelable protective finish and preparation method thereof |
| CN104761960A (en) * | 2015-03-21 | 2015-07-08 | 广东南海启明光大科技有限公司 | 3D curved surface shielding liquid capable of spraying and thermocuring and preparation method thereof |
| CN105838276A (en) * | 2016-01-29 | 2016-08-10 | 宁波吉象塑胶制品有限公司 | Adhesive tape preparation method |
| CN105838276B (en) * | 2016-01-29 | 2018-09-21 | 宁波吉象塑胶科技股份有限公司 | A kind of preparation method of adhesive tape |
| CN108034163A (en) * | 2017-12-05 | 2018-05-15 | 沈阳化工股份有限公司 | A kind of PVC vehicle glasses anti-fog film and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103467890B (en) | 2016-04-20 |
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